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FOOD FREEZING

Mechanisms, Food Quality, and


Engineering Aspects

Understanding Freezing
Retard deterioration of foods - preservation
Chemical, physical, microbial, etc.
Improve organoleptic properties
Desirable characteristics
Controlling Freezing
Maximal quality of product
Initial freezing process
Storage and distribution conditions
Efficient and economic processing
Food Freezing
For a food to freeze, must lower the temperature
below its freezing point
Foods are mixtures of various ingredients, some
of which affect phase behavior of water
Sugars, salts, proteins, fats, flavors, etc.
Freezing point depression
Dependent on composition
Particularly smaller molecular weight
ingredients like sugars and salts
Average freezing point of some food categories
Food Moisture
content (%)
T
f
,
o
C
Vegetables 78 - 92 -0.8 to -2.8
Fruits 87 - 95 -0.9 to -2.7
Apple juice 87.2 -1.44
Apple sauce 82.8 -1.67
Apple Juice concentrate 49.8 -11.3
Meat 55 - 70 -1.7 to -2.2
Milk 87 -0.5
Egg 74 -0.5
Freezing Process
As freezing proceeds, heat is released and
concentration of unfrozen liquid phase increases
Phase change (333.2 kJ/kg of ice) causes
temperature of local environment to increase
Temperature increase depends on amount
of ice freezing and the rate of heat
removal
Freeze concentration of remaining fluid phase
causes decrease in freezing point of remaining
liquid
Freezing Point Depression
-6
-5
-4
-3
-2
-1
0
0 10 20 30 40
F
r
e
e
z
i
n
g

P
o
i
n
t
,

C

Concentration, %
Glucose
Sucrose
Corn Syrup
Freezing Process
As more heat is removed, the unfrozen phase
continues to become more concentrated
Continued freezing causes decrease in
molecular mobility (increase in viscosity of
unfrozen phase)
Molecules move more slowly
Approaches glassy state where molecular
mobility is very low
Freezing Process
The endpoint of freezing is either:
When freezing point temperature reaches freezer
temperature
Product temperature goes below the glass
transition temperature and the unfrozen phase
becomes glassy
A state diagram helps understand which will
occur
Follow trajectory of freezing process
State Diagram
State diagrams tell us where to expect the system
to head for phase equilibrium
At a given storage temperature, the system will
move to approach the equilibrium curve
Maximum amount of ice formed
Any point other than on the freezing point
depression curve, including the glassy state, is
nonequilibrium - metastable
Stability depends on process/storage conditions
Freezing Rate
But freezing rate determines how much of the
allowable water freezes in a food
Slow freezing - equilibrium ice formation
Follows freezing point depression
Fast freezing - any amount of ice, depending
on freezing rate
Any trajectory
Water Frozen
Amount of water frozen into ice thus depends on
freezing rate
Slow freezing - maximum ice
Fast freezing - any ice content
Unfreezable Water
assuming phase equilibrium
All products have some water that remains
unfrozen even at very low temperatures (<-40C)
Meat, fish
a
8-12%
Liquid eggs
a
7%
fruit juice
a
3%
spinach
a
2%
white bread
a
46%
bread @ -18C
b
25%
a
Zaritzky, 2000
b
Kennedy, 2000
Both in CJ Kennedy, Managing Frozen Foods (2000)
Freezing Rate
Due to conduction heat transfer, the freezing
rate is also a function of the position in the
food
Center sees much slower freezing rate than surface
Mechanisms of freezing may be different
Ice distribution may also be different at surface from interior
Temperature differential allows moisture migration
Freezing Rate
Freezing rate defined as:
Ratio between the minimum distance from the surface to
the thermal center, and the time elapsed between the
surface reaching 0C and the thermal center 10C colder
than the temperature of initial ice formation. (International
Institute of Refrigeration, as quoted by Zaritzky, 2000)

Typical food freezing rates
0.2 - 0.5 cm/h slow static
0.5 - 3 cm/h quick air blast and plate
5 - 10 cm/h rapid IQF fluidized bed
10-100 cm/h ultra-rapid cryogenic
Question
Freezing rate has many impacts on a freezing
operation - how many can you list?
Product quality
Throughput rate
Refrigeration costs
Equipment costs
Others?
Freezing Mechanisms
The process of freezing requires these steps:
Subcooling - bring temperature down below
freezing temperature
Nucleation - formation of the smallest crystals
from the liquid state
Growth - increase in size of those nuclei until the
system approaches phase equilibrium
Ripening - change in dispersion of crystal sizes
with time due to thermodynamic effects
Subcooling
Nuclei do not form under most circumstances
until temperature is lowered substantially
below the melting point (T
m
)
Related to an energy barrier to be overcome to form
a stable nucleus
The temperature at which nuclei form depends on
process conditions
Cooling rate, agitation, etc.
Subcooling
High T (20-30C)
Rapid freezing
High nucleation rate
Many nuclei formed

Low T (1-5C)
Slower freezing
Lower nucleation rate
Fewer nuclei formed
T = the difference between freezing point and freezing temperature
Nucleation
Onset of nuclei formation in a frozen food is
when the water molecules attain the correct
energy and position to form into a crystal
lattice
Nucleation Mechanisms
Homogeneous nucleation - water molecules cluster together
Heterogeneous nucleation - dust particles promote nucleation
Growth
After nuclei form, they grow until all
subcooling has been relieved
Equilibrium temperature and product temperature are the same
Mechanisms
Heat removal rate
Counter-diffusion of solutes
Effects of Freezing
on Food Quality
Numerous changes take place during all stages
of freezing that can affect food quality
Prefreezing conditions
Freezing rate
Storage conditions
Prefreezing
If initial temperature is well above the freezing
point when a product is frozen
Water migration occurs due to thermal gradients
during cooling and freezing
The warm water inside migrates toward surface
Redistribution of solutes
May be a problem in regions of different water
content, e.g., crumb and crust
Can cause separation and unsightly appearance
Freezer Bloom
Freezing of frozen cakes with sugar frosting
Freezing from warm state causes water
migration, which carries dissolved sugar
When the water evaporates (or ice
sublimes) leaves unsightly spots
Freezing
Freezing affects properties of the food
Effects on cell structure
Osmotic pressure differences between intracellular and
extracellular fluid cause moisture migration
o May lead to cell lysis (rupture)
Moisture migration
Osmotic differences; thermal gradients; etc.
Volume expansion of ice may rupture cells
Freeze concentration of solutes in unfrozen phase
Salts, sugars, etc. may lead to crystallization
Protein denaturation
Freeze concentration of solutes like salts
Slow vs. Rapid Freezing
Rapid freezing leads to formation of many
more and smaller crystals
Fewer internal changes in structures (cells,
etc.)
Smoother product
Freezer Storage
Over time, changes can occur in the frozen
product that cause product quality to
deteriorate
Equilibration of ice phase volume
Changes in ice crystal dispersion due to ripening
Starch retrogradation
Protein denaturation
Water migration and loss
Phase Equilibration
If phase equilibrium was not attained during
freezing, the system will drive towards that
equilibrium over time if T > Tg
Increase in ice content
Changes in ice crystal
size distribution
Recrystallization
Definition:
"Any change in the number, size, shape, orientation
or perfection of crystals following completion of
initial solidification." (Fennema, Powrie and Marth,
1973)
Enhanced ramatically
by fluctuating
temperatures during
storage

Fluctuation in Ice Content
Recrystallization
Effects of recrystallization
Increase in mean size causes disruption of
microstructure and loss of texture
Smooth frozen product becomes coarse
Moisture Migration and Freezer Burn
During freezing and frozen storage, regions of
different water activity tend to equilibrate
Crust and crumb will change during storage
Bread and icing or filling
Pizza crust and sauce
Freezer burn - color and quality change
Loss of moisture to air
Summary
An understanding of the physico-chemical
factors that affect quality during freezing
allows production of the highest quality
product with the most efficient process
Engineering Aspects
Freezing process has a dramatic affects on the
thermal properties of food products
As the water within the product changes from
liquid to solid, the density, thermal
conductivity, heat content (enthalpy), and
apparent specific heat change gradually as the
temperature decreases below the initial
freezing point for water in the food.
Density
The density of solid water (ice) is less than the
density of liquid water. Thus the density of a frozen
food will be less than the unfrozen product.
950
960
970
980
990
1000
1010
1020
1030
1040
1050
1060
-45 -35 -25 -15 -5 5 15 25
P
r
o
d
u
c
t

D
e
n
s
i
t
y
,

k
g
/
m
3

Temperature, C
Strawberries
Water content 89.3%
Init. Freezing temp = -0.89C
Thermal Conductivity
Thermal conductivity of ice is approximately four time larger
than that of liquid water.
This relationship has a similar influence on the thermal
conductivity of frozen food.
The majority of thermal conductivity increase occurs within
10
o
C below the initial freezing temperature of the product.
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
-40 -30 -20 -10 0 10
T
h
e
r
m
a
l

C
o
n
d
u
c
t
i
v
i
t
y
,

W
/
m
-
o
C

Temperature, C
Froozen lean beef
Enthalpy
The heat content (enthalpy) of a froozen food is an important property in
computations of refrigeration requirement for freezing of product.
The heat content normally zero at -40C and increases with increasing
temperature.
Significant changes in enthalpy occur at 10
o
C below the initial freezing
temperature, when most of the phase change in product water occurs.
0
50
100
150
200
250
300
350
400
-45 -35 -25 -15 -5 5 15
E
n
t
h
a
l
p
y

(
k
J
/
k
g
)

Temperature, C
Sweetcheries
Moisture content = 77%
Init. Freezing temp. = -2.61C
Apparent Specific heat
Specific heat of a frozen food at a temperature greater than
20
o
C below the initial freezing point is not significantly
different from the specific heat of the unfrozen product.
0
5
10
15
20
25
30
35
-45 -35 -25 -15 -5 5 15
A
p
p
a
r
e
n
t

S
p
e
c
i
f
i
c

H
e
a
t
,

k
J
/
k
g
.
o
C

Temperature, C
Sweet cherries
Moisture content = 77%
Init.freezing temp. = -2.61
o
C
Freezing Process
Prefreezing
Phase change
Postfreezing
Prefreezing : The temperature of the water
decreases to the freezing point as sensible heat is
removed. Small amount of supercooling take
place; but once nucleation occurs and ice crystals
begin to form, the freezing point increases to 0
o
C.
Phase change : The temperature remains at the
freezing point until a complete phase change
occurs. Latent heat of fusion is removed from
liquid water to convert it into solid ice.
Postfreezing : When all the liquid water has
changed into solid ice, the temperature of the ice
decreases rapidly as sensible heat is removed.
Freezing Process of Pure Water
Prefreezing : Temperature decreases during prefreezing
as sensible heat is removed. Nucleation and ice crystals
begin to form at lower temperature that that of pure
water.
Phase change : After a brief supercooling, latent heat is
gradually removed with decreasing temperature. This
is due to concentration effect during freezing of food.
As water in the food converts into ice, the remaining
water becomes more concentrated with solutes and
depresses the freezing point.
After this time, sensible heat is further removed until
preselected endpoint is reached (Typically -18
o
C for
fruits and vegetables and -25
o
C for foods with higher
fat contents such as ice cream, fatty fish, ect.)
Freezing Process of Potato
Freezing Time
The most important calculation in the design
of freezing process is the determination of
freezing time.
Freezing time is the most critical factor
associated with the selection of a freezing
system to ensure optimum product quality.
Freezing time requirements help establish
system capacity.
Methods of prediction : Planks Equation and
Phams Method.

Planks Equation
Proposede by Plank (1913) and adapted to food by
Ede (1949).
This equation describes only the phase change
period of the freezing process.
Planks Equation
Assume the homogeneous slab is
at initial freezing temperature (T
F
).
The slab is exposed to a freezing
merdium at temperature T
a
.
After some time, the will be 3
layers; 2 frozen layers at the
surface and a middle unfrozen
layer.
The moving front inside the slab
separates the frozen from the
unfrozen region.
As water is converted into ice at
the moving front, latent heat of
fusion (L) is generated.
The latent heat of fusion generated at the
moving front must be transfered through the
frozen layer to the surface (by conduction).
The heat is then transfered to the freezing
medium via convection. The convective heat
transfer coefficient at the surface of the slab is
h.
The temperature of the unfrozen region
remains at T
F
until the freezing front moves all
the way to the center plane of the food.
Formulation of Planks Equation
Two layers of heat transfer : conduction through the
frozen layer and a convective boundary layer.
Formulation of Planks Equation
A k
X q
T T
X
T T A k
q
s F
F s
cond
.
) (
) ( . A
=
A

=
A h
q
T T T T A h q
a s a s conv
.
) ( ) ( . = =
|
.
|

\
|
+
A
= +
h k
X
A
q
T T T T
a s s F
1
) ( ) (
k
X
h
T T A
q
a F
A
+

=
1
) (
The heat released due to advancement of the
freezing front :


where :
A = cross section area, m
L = latent heat of fusion, kJ/kg

f
= density of water, kg/m
3

dx/dt = velocity of moving front, m/s
Formulation of Planks Equation
dt
dx
L A q
f
=
Since all the heat released at the freezing front must be
transfered out to the surrounding medium, then :



The freezing process is completed when the moving front
advances to the center of the slab (a/2). Then
Formulation of Planks Equation
k
X
h
T T A
dt
dx
L A
a F
f
A
+

=
1
) (

} }
(
(

=
2 /
0 0
1
a
f a F
f
t
dx
k
x
h T T
L
dt
f

(
(

=
f a F
f
f
k
a
h
a
T T
L
t
8 2
2

Freezing time for


infinite slabs
For food material with moisture content m,
Planks equation becomes :
Formulation of Planks Equation
(
(

=
f a F
f
f
k
a
h
a
T T
m L
t
8 2
2

Where :
L = latent heat of fusion for water (333.2 kJ/kg)
m = moisture content of food, fraction

f
= density of frozen product, kg/m
3

T
F
= freezing temperature, C
T
a
= medium temperature, C
a = thickness of the slab, m
h = convective coefficient, W/m
2
.K
k
f
= thermal conductivity of frozen product, W/m.K
General Form of Planks Equation



where :

f
= density of the frozen maerial
k
f
= conductivity of frozen material
P and R = shape factors

Formulation of Planks Equation
|
|
.
|

\
|
+

=
f a F
f
f
k
a R
h
a P
T T
m L
t
2
'. '.
. .
Values for P and R
Infinite slab : P = R = 1/8
Infinite cylinder: P = R = 1/16
Sphere : P = 1/6 R = 1/24

For finite slab and cylinder, use diagram to
determine the values for P and R.
Material geometry constants P and R for a brick-shaped object for the Planks Freezing
time equation with dimensions a, b, c; where a is the shortest side.
Example #1
A spherical food product is being frozen in an air-
blast freezer. The initial rpoduct temperature is 10
o
C
and the cold air -40
o
C. The product has a 7 cm
diameter with density of 1000 kg/m
3
, the initial
freezing temperature is -1.25
o
C, the thermal
conductivity of the frozen product is 1.2 W/m.K, and
the latent heat of fusion is250 kJ/kg. Convective heat
transfer coefficient is 50 W/m
2
.K. Compute the
freezing time.
Given:
T
i
= 10
o
C
T
a
= -40
o
C
T
F
= -1.25
o
C
a = 0.07 m

f
= 1000 kg/m
3

k
f
= 1.2 W/m.K
H
L
= 250 kJ/kg
P = 1/6
R = 1/24
Example #1
Using Planks Equation :

Example #1
hour s W J t
K m W
m
K m W
m
x
C
kg kJ m kg
t
F
o
F
72 . 0 2600 / 2600
) . / 2 . 1 ( 24
) 07 . 0 (
) . / 50 ( 6
07 . 0
)] 40 ( 25 . 1 [
) / 250 ( ) / 1000 (
2
3
= = =
(

+

=
Blueberries are to be frozen in 2 liters cardboard boxes having the
following dimensions: 6 cm x 15 cm x 22.5 cm
Blueberries have the following characteristics:
moisture content m = 85%
Density = 1015 kg/m
3

Thermal conductivity
frozen: k
f
= 1.95 W/m.K
unfrozen: k
u
= 3.85 W/m.K

Freezing temperature: T
f
= - 0.9C
The boxes are made of cardboard 0.8 mm thick with a thermal
conductivity k
card
= 0.05 W/m.K
The blueberries are frozen in an air blast freezer where the
convective heat transfer coefficient (h
c
) between the cold air and
the boxes surface is equal to 25 W/m
2
.K.

The temperature of the cold air in the freezer can be adjusted
between -20C and -40C.
Example #2
Box dimensions: 0.06 m x 0.15 m x 0.225 m
a = 0.06 m b = 0.15 m c = 0.225 m
b/a = 2.5 c/a = 3.75

Example #2
From above chart we get: R = 0.085 P = 0.304

Evaluation of the overall heat transfer coefficient:




= 1/25 + 0.8 x 10
-3
/0.05 = 0.056


U = 17.86 W/m
2
.K
k
f
= 1.95 W/m.K

Latent heat of fusion for blueberries = 85% x latent heat of fusion of water
L . m = 335 x 0.85 = 284.75 kJ/kg = 284750 J/kg

We want the blueberries to freeze in less than 2.5 hours: q
f
= 2.5 x 3600 = 9000 s

Example #2
Example #2
C T
x x x
k
a R
U
a P
t
m L
T T
k
a R
U
a P
t
m L
T T
o
a
f f
f
F a
f f
f
a F
7 . 38
95 . 1
06 . 0 085 . 0
86 . 17
06 . 0 304 . 0
9000
1015 284750
9 . 0
' '
. .
' '
. .
2
2
2
=
(

+ =
(
(

+ =
(
(

+ =

Phams Method
Proposed by Q. T. Pham in 1986
Can be used for finite-size objects of irregular
shapes by approximating them to be similar to
an ellipsoid.
Easy to use yet provides answer with
reasonable accuracy.
Basic Assumptions:
Environmental conditions are constant
Initial temperature, T
i
is constant
Final temperature, T
c
is fixed
Convective heat transfer at the surface of
the object obeys Nowtons law of cooling
Phams Method
Cooling and Freezing Diagram
Based on experimental data for variety of foods


where T
c
is final center temperature and T
a
is medium
temperature.
Freezing time for simple-shaped objects :




where d
c
is the shortest distance to the center, or radius. h is
convective heat transfer coefficien, E
f
is shape factor (E
f
= 1 for
infinite slab, 2 for infinite cylinder, and 3 for sphere


Phams Method
a c fm
T T T 105 . 0 263 . 0 8 . 1 + + =
|
.
|

\
|
+
(

A
A
+
A
A
=
2
1
2
2
1
1 Bi
f
c
N
T
H
T
H
h E
d
t
k
l h
N
Bi
.
=